Realizing High Capacity and Zero Strain in Layered Oxide Cathodes via Lithium Dual-Site Substitution for Sodium-Ion Batteries

Zhonghan Wu; Youxuan Ni; Sha Tan; Enyuan Hu; Lunhua He; Jiuding Liu; Machuan Hou; Peixin Jiao; Kai Zhang; Fangyi Cheng; Jun Chen

doi:10.1021/jacs.3c00117

Realizing High Capacity and Zero Strain in Layered Oxide Cathodes via Lithium Dual-Site Substitution for Sodium-Ion Batteries

J Am Chem Soc. 2023 May 3;145(17):9596-9606. doi: 10.1021/jacs.3c00117. Epub 2023 Apr 14.

Authors

Zhonghan Wu¹, Youxuan Ni¹, Sha Tan², Enyuan Hu², Lunhua He^{3

4

5}, Jiuding Liu¹, Machuan Hou¹, Peixin Jiao¹, Kai Zhang^{1

6}, Fangyi Cheng^{1

6}, Jun Chen^{1

6}

Affiliations

¹ Frontiers Science Center for New Organic Matter, Renewable Energy Conversion and Storage Center (RECAST), Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071, P. R. China.
² Chemistry Division, Brookhaven National Laboratory Upton, New York 11973, United States.
³ Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, P. R. China.
⁴ Songshan Lake Materials Laboratory, Dongguan 523808, P. R. China.
⁵ Spallation Neutron Source Science Center, Dongguan 523803, P. R. China.
⁶ Haihe Laboratory of Sustainable Chemical Transformations, Tianjin 300192, P. R. China.

PMID: 37058227
DOI: 10.1021/jacs.3c00117

Abstract

Sodium-ion batteries have garnered unprecedented attention as an electrochemical energy storage technology, but it remains challenging to design high-energy-density cathode materials with low structural strain during the dynamic (de)sodiation processes. Herein, we report a P2-layered lithium dual-site-substituted Na_0.7Li_0.03[Mg_0.15Li_0.07Mn_0.75]O₂ (NMLMO) cathode material, in which Li ions occupy both transition-metal (TM) and alkali-metal (AM) sites. The combination of theoretical calculations and experimental characterizations reveals that Li_TM creates Na-O-Li electronic configurations to boost the capacity derived from the oxygen anionic redox, while Li_AM serves as LiO₆ prismatic pillars to stabilize the layered structure through suppressing the detrimental phase transitions. As a result, NMLMO delivers a high specific capacity of 266 mAh g^-1 and simultaneously exhibits the nearly zero-strain characteristic within a wide voltage range of 1.5-4.6 V. Our findings highlight the effective way of dual-site substitution to break the capacity-stability trade-off in cathode materials for advanced rechargeable batteries.